JP2019034253A - Printing method on long body - Google Patents

Abstract

To provide a manufacturing method of a laminate film hardly generating crack on the end of a TD direction (width direction).SOLUTION: In a printing method on a long body for forming one or more belt-like coating films extending in a longer direction excluding both ends in the width direction, on at least one surface of the long body comprising, preferably, a super birefringence resin having a tensile strength in the longer direction of 100 MPa or less, coating liquid for forming the coating film is printed in the shape of a long belt by using a gravure roll including, over the whole circumference on the outer peripheral surface, a concave part provided corresponding to a position where a pre-coated film is formed in the range from the end to the end in the width direction of the long body.SELECTED DRAWING: Figure 10

Description

  The present invention relates to a method for printing on a long body, and more particularly to a method for printing a coating film for forming a cured layer on a resin film as a long body in the production of a laminate film having a cured layer such as an antiglare layer. .

  In recent years, a technique for installing a “touch panel” on the surface of a flat panel display (FPD) included in electronic devices such as mobile phones, portable electronic document devices, vending machines, car navigation systems, etc. has begun to spread. The “touch panel” can be roughly classified into a resistance type and a capacitance type. The “resistance type” touch panel has a transparent substrate made of a resin film and an X coordinate (or Y coordinate) provided on the substrate. ) A main part is composed of a detection electrode sheet, a Y-coordinate (or X-coordinate) detection electrode sheet, and an insulator spacer provided between these sheets.

  These X-coordinate detection electrode sheet and Y-coordinate detection electrode sheet are usually separated by an insulator spacer, but when pressed with a pen or the like, the two coordinate detection electrode sheets are in electrical contact with each other at that portion. As a result, the position (X coordinate, Y coordinate) touched by the pen can be detected. If the pen is moved, the coordinates are recognized each time, and finally a character can be input. Yes.

  On the other hand, the “capacitance type” touch panel has an X-coordinate (or Y-coordinate) detection electrode sheet and a Y-coordinate (or X-coordinate) detection electrode sheet laminated on an insulating sheet, and further glass on It has a structure in which an insulator such as is arranged. When a finger is brought close to an insulator such as glass, the capacitance of the X-coordinate detection electrode and the Y-coordinate detection electrode in the vicinity changes, so that the position can be detected.

  As a conductive material for an electrode having a predetermined circuit pattern in the electrode sheet (also referred to as an electrode substrate film), a transparent conductive material such as ITO (indium oxide-tin oxide) as disclosed in Patent Document 1 has been conventionally used. Membranes are widely used. In addition, with an increase in the size of a touch panel, a metal film having a mesh structure made of a thin metal wire as disclosed in Patent Document 2, Patent Document 3, and the like has begun to be used.

  When the above transparent conductive film is compared with a thin metal wire (metal film), the transparent conductive film has an advantage that the circuit pattern such as an electrode is hardly visually recognized because of its excellent transparency in the visible wavelength region. Since the electric resistance value is higher than that of (metal film), there is a disadvantage that is not suitable for increasing the size of the touch panel and increasing the response speed. On the other hand, metal thin wires (metal films) are suitable for increasing the size of touch panels and increasing the response speed because of their low electrical resistance, but they have high reflectivity in the visible wavelength region, so they are processed into a fine mesh structure. However, the circuit pattern may be visually recognized under high-intensity illumination, which has the disadvantage of reducing the product value.

  Therefore, in Patent Document 4 and Patent Document 5, a metal oxide is formed between a transparent substrate made of a resin film and a metal film of the metal thin wire in order to make use of the characteristics of the metal thin wire (metal film) having a low electric resistance value. A method of reducing the reflection of metal fine wires (metal film) observed from the transparent substrate side through a metal absorption layer (also referred to as a blackened film) made of is disclosed.

  In the production of an electrode sheet provided with a metal absorption layer made of this metal oxide, it is usually reacted on the surface of a continuously conveyed long resin film from the viewpoint of increasing the efficiency of film formation of the metal oxide. After a metal absorption layer is continuously formed by reactive sputtering using a metal target (metal material) in an inert gas atmosphere, sputtering is performed using a metal target (metal material) such as copper in an inert gas atmosphere. Thus, a metal layer is continuously formed on the metal absorption layer, thereby producing a laminate film that becomes a base material of the electrode substrate film. Then, the laminated film composed of the metal absorption layer and the metal layer is etched with an etching solution such as a cupric chloride aqueous solution or a ferric chloride aqueous solution, so that an electrode is formed on the laminated film (metal absorption layer and metal layer). A circuit pattern such as the above is patterned.

  Therefore, the laminate film as the base material of the electrode substrate film has a characteristic that the metal absorption layer and the metal layer constituting the laminate film are easily etched by an etching solution such as a cupric chloride aqueous solution or a ferric chloride aqueous solution. Therefore, it is required that a circuit pattern such as an electrode patterned by the etching has a characteristic that it is difficult to be seen under high luminance illumination. The above metal layer is made thicker as necessary by using a wet plating method such as electrolytic plating. Moreover, the said laminated film is also formed into a film on both surfaces by performing the same process on the surface and back surface of a long resin film.

JP 2003-151358 A JP 2011-018194 A JP 2013-0669261 A JP 2014-142462 A JP 2013-225276 A

  By the way, in the laminated structure in which the laminated films 2 patterned on both surfaces of the transparent substrate 1 made of a PET film are provided as shown in FIG. 1, the laminated film 2 is counted from the transparent substrate 1 side as the first layer. In the case of the metal absorption layer 3 formed by the sputtering method of the eye, the metal layer 4 formed by the sputtering method and the wet plating method of the second layer, and the metal absorption layer 5 formed by the sputtering method of the third layer, The regular reflection R2 of the third metal absorption layer 5 on the front side has a lower reflectance than the regular reflection R1 of the first metal absorption layer 3 on the back side. This is because the third-layer metal absorption layer 5 is formed on the second-layer metal layer 4 by a wet plating method having a rough surface, so that the reflected light is easily scattered. Thus, even if the first layer and the third metal absorption layer are formed by sputtering using the same material under the same film formation conditions, the first layer metal on the back side to be observed through the transparent substrate. There was a problem that the reflection of the absorption layer was conspicuous.

  In addition, when a PET film is used as the transparent substrate of the electrode substrate film, there is a problem that rainbow unevenness occurs due to its birefringence, or that it becomes dark when used with polarized sunglasses. As a countermeasure against this, in recent years, a super birefringent film has been adopted as a transparent substrate. However, the super birefringent film has a feature that the breaking strength in the MD direction (length direction) due to the manufacturing method is small, and it is easy to tear in the TD direction (width direction).

  Furthermore, in order to suppress the above-mentioned problem that the reflection of the first metal absorption layer on the back surface side is conspicuous, anti-glare coating treatment is applied to the surface of the resin film to increase the diffuse reflection by forming innumerable irregularities on the surface. There are things to do. However, when a super-birefringent film is used for the transparent substrate and antiglare coating treatment is applied to at least one surface thereof, as shown in FIG. 2, cracks C are formed at the end of the super-birefringent film 6 in the TD direction (width direction). May occur easily.

  The present invention has been made in view of the above-described conventional problems, and even in the case where a coating film such as an antiglare coat is formed on one side or both sides of a long body such as a super birefringent film, the TD direction is provided. It aims at providing the printing method of the coating film to a elongate body which can suppress that a crack generate | occur | produces in the edge part of (width direction).

  In order to achieve the above-mentioned object, the printing method for a long body of the present invention comprises at least one strip-like strip extending in the longitudinal direction excluding both ends in the width direction on at least one surface of the long body. A method of printing on a long body for forming a coating film, the concave portion provided corresponding to a position where a front coating film is formed from end to end in the width direction of the long body The coating liquid which forms the said coating film is printed on the said elongate belt using the gravure roll which provided the outer peripheral surface over the perimeter.

  According to the present invention, even when a long body on which a hardened layer such as an anti-glare coat is formed is handled by conveyance by roll-to-roll, the problem of breakage or cracking can be made difficult to occur.

It is sectional drawing which shows typically the mode of reflection of the reflected light of the conventional laminated structure which has the laminated film by which patterning was carried out on both surfaces of the resin film. It is a top view which shows typically the crack generation state of the conventional super birefringent resin film in which the anti-glare layer was formed. It is sectional drawing which shows the measuring method of the haze value of a to-be-measured object. It is sectional drawing explaining the influence which the size of the filler of an anti-glare layer has on a haze value. It is sectional drawing explaining the mode of the crack generation by the bending of the resin substrate provided with the anti-glare layer. It is a front view which shows one specific example of the coating apparatus which can implement the printing method of the elongate body of this invention. It is a top view at the time of forming an anti-glare layer in a resin film for two strips using a general gravure roll in the coating device of FIG. It is a perspective view of the gravure roll used suitably in the printing method of this invention. It is a top view at the time of forming an anti-glare layer in the resin film for two strips using the gravure roll of FIG. It is a front view which shows the other specific example of the coating apparatus which can implement the printing method of the elongate body of this invention. It is a perspective view of the film thickness adjustment rod used suitably for the coating apparatus of FIG. It is sectional drawing which shows typically the mode of reflection of reflected light in case the laminated film patterned by the both sides of the resin film by which the anti-glare process was provided. It is a front view of the vacuum film-forming apparatus used suitably in the case of preparation of a laminated body film. It is typical sectional drawing of the laminated body film which has a 1st metal absorption layer and a 2nd metal layer on both surfaces of the transparent substrate which consists of a resin film coat | covered with the anti-glare layer from the transparent substrate side. It is typical sectional drawing of the laminated body film which has the metal layer laminated | stacked on the metal layer of FIG. 14 with the wet film-forming method. FIG. 16 is a schematic cross-sectional view of a laminate film obtained by forming a second metal absorption layer as a third layer on the thickened metal layer in FIG. 15. FIG. 17 is a schematic cross-sectional view of an electrode substrate film having metal laminated thin wires obtained by patterning the laminate film of FIG. 16 on both surfaces of a transparent substrate.

  Hereinafter, as a specific example of the method for printing on a long body according to the present invention, a case where a laminate film in which a laminate is formed on a long resin film as a long body is described as an example in detail. explain. This laminate film is composed of a transparent substrate made of a long resin film having an anti-glare coat layer formed on the back surface formed by the printing method of one specific example of the present invention, and a laminate film provided on both surfaces of the transparent substrate. The laminated film formed on each surface includes a first metal absorption layer, a second metal layer, and a third metal absorption layer as counted from the transparent substrate side.

  The material of the resin film is not particularly limited. For example, polyethylene terephthalate (PET), polyethersulfone (PES), polyarylate (PAR), polycarbonate (PC), polyolefin (PO), triacetylcellulose (TAC) and It can be selected from resin materials such as norbornene. When norbornene is selected as the resin material, representative examples include ZEONOR (trade name) manufactured by ZEON Corporation and ARTON (trade name) manufactured by JSR Corporation. In addition, when producing the electrode substrate film mainly used for "touch panel" from the laminated body film produced by the following method, the thing excellent in transparency in the visible wavelength region among the resin materials is desirable. Further, when a super birefringent film having a tensile strength in the MD direction (longitudinal direction) (conforming to JIS K 7127 1999) of about 100 MPa or less is used, a remarkable effect is exhibited.

  As described above, the resin film used for the laminate film is a composite having a structure in which the back surface is covered with the antiglare layer. Thereby, in the electrode substrate film obtained by patterning processing such as etching on the laminate film, the first layer formed on the back surface of the resin film subjected to the anti-glare treatment is wet. Since the film is formed on the rough surface in the same manner as the third layer formed on the second layer formed by the plating method, when the circuit pattern on the back side is viewed from the front side, the resin film Since the scattering of incident light through the surface increases as in the front surface side, the specular reflection component on the back surface side can be reduced as in the front surface side.

  The antiglare layer formed on at least one surface of the transparent substrate made of a resin film as described above is preferably a hard coat layer (cured layer) that is harder than the resin film. The layer thickness is appropriately set according to the desired optical properties, but in general, the layer thickness is preferably 0.5 μm or more and 30 μm or less, and more preferably equal to or more than the diameter of the fine particles to be used. This antiglare layer is composed of resin and fine particles. As the resin, an ultraviolet curable urethane resin or acrylic resin is preferably used. An inorganic sol such as a silica sol having a particle size of 500 nm or less may be added to the antiglare layer, whereby the hardness of the antiglare layer can be controlled.

  The particle diameter of the fine particles contained in the antiglare layer is preferably in the range of 0.5 to 20 μm and within twice the thickness of the resin layer. The fine particles are preferably blended at a ratio of 1 to 50 parts by mass with respect to 100 parts by mass of the resin. The specific particle size of the fine particles and the blending ratio are appropriately determined in consideration of the desired surface roughness Ra and haze value of the antiglare layer. In general, the surface roughness Ra of the antiglare layer is preferably 0.1 μm or more in order to lower the reflectance of the laminated film (metal absorption layer). As will be described later, the haze value is preferably low. However, when the surface roughness Ra of the antiglare layer is set to 0.1 μm or more, the haze value is 2.5% even if the fine particles contained in the antiglare layer are arbitrarily selected. That's it.

  As the above fine particles, inorganic fine particles or organic fine particles can be used. The inorganic fine particles can be selected from silicon oxide fine particles, titanium oxide fine particles, aluminum oxide fine particles, zinc oxide fine particles, tin oxide fine particles, calcium carbonate fine particles, barium sulfate fine particles, talc fine particles, kaolin fine particles, calcium sulfate fine particles, etc. Organic fine particles include polymethyl methacrylate resin powder (PMMA fine particles), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, polyester resin powder, It can be selected from polyamide resin powder, polyimide resin powder, polyfluorinated ethylene resin powder, and the like.

As an evaluation method of the above antiglare treatment, there is a haze measurement method (JISK7136 2000). This method is a haze value that is the ratio of the scattered light transmittance measured without blocking the transmitted light to the total light transmittance measured by blocking the transmitted light of the integrating sphere with the measurement object fixed by the diffuser plate. It is something to evaluate. Specifically, referring to the schematic diagram of the haze measurement method shown in FIG. 3, the test piece s of the PET film (transparent substrate) subjected to the antiglare treatment is fixed to the light incident side of the integrating sphere h and the integrating sphere The other end side opening of h is closed by the diffusion plate i, the light j is made incident, and the light reflected in the integrating sphere h by multiple reflection is measured by a light receiver k provided below the integrating sphere. Measure the “transmittance” T ₀ . Next, the other end side opening of the integrating sphere h is not closed by the diffuser plate i, and the light j is again incident in the same manner, and the light reflected in the integrating sphere h is reflected (however, the light transmitted through the opening). Is not included) and the “scattered light transmittance” T ₁ is measured by the light receiver k. And haze value (%) is calculated | required from the following formula 1.

[Formula 1]
Haze value = (T ₁ / T ₀ ) × 100

  As described above, when an electrode substrate film for a touch panel is produced from a laminate film, the haze value of the antiglare layer provided on one side of the transparent substrate is desirably 10% or less. This is because when the haze value of the antiglare layer exceeds 10%, the image of the flat panel display observed through the touch panel may be clouded to deteriorate visibility (transmittance). In particular, when the laminated film of the laminate film is etched and patterned into an electrode substrate film, an image of the flat panel display is observed through the antiglare layer on the transparent substrate from which the laminated film has been removed by etching. Therefore, the haze value of the antiglare layer provided on the transparent substrate is desirably 10% or less.

  The haze value of the transparent substrate subjected to the antiglare treatment is mainly determined by the particle size (particle size) and density (particle density) of the fine particles 9 included in the antiglare layer 8 on the transparent substrate 7 as shown in FIG. The haze value increases as the particle size of the fine particles 9 increases and the particle density increases. In the case where fine particles 9A having an excessively large particle size are employed as shown in the upper diagram of FIG. 4, when the metal film is formed by patterning the laminated film, the metal mesh is touched (circuit pattern of the mesh structure). It is necessary to be careful since a gap may be generated when the metal mesh is bonded to another film or the like in a subsequent process of manufacturing as a touch panel having a touch panel.

  In addition, the metal mesh is not only used in a planar form, but may be used in a curved form or folded or opened. The coating agent used for the anti-glare layer is generally of a type having a surface hardness (conforming to JIS K5600-5-4 1999) of 2H or higher after curing (in a usable state), as shown in the left side of FIG. When the hardened layer 8 is formed on the transparent substrate 7 with a hard coating agent, it may break during bending.

  Therefore, in order to make it difficult to break as shown in the right side view of FIG. 5, it is preferable to form a soft hardened layer 8 having a pencil hardness of about HB to H on the transparent substrate 7 after curing (in a usable state). In this case, if the scratch hardness (pencil hardness) of the anti-glare layer in accordance with JIS K5600-5-4 1999 satisfies the condition of H or less, “mechanical properties of coating film” defined in JIS K5600-5-1 1999- In “bending resistance (cylindrical mandrel method)”, a mandrel diameter of 2 mmφ or less can be realized.

  When producing this laminate film, an antiglare layer is formed so that the surface of the transparent substrate is exposed at both ends in the TD direction of the long transparent substrate. That is, both ends in the width direction of the transparent substrate are not covered with the antiglare layer. Thereby, when handling a laminated body by conveyance etc. by a roll-to-roll system, it becomes difficult to produce the problem that an anti-glare layer fractures | ruptures or breaks. In addition, although rolls having various diameters are used for conveyance in the roll-to-roll system, the holding angle (the angle at which the film contacts the outer peripheral surface of the roll) that causes breakage or cracking is 90 ° or more. There is a small diameter roll having a diameter of about 70 mm. It is preferable that an exposed portion not covered with the antiglare layer at each end portion in the TD direction of the transparent substrate has a width of 1 mm or more and 10 mm or less. If this width is less than 1 mm, it becomes difficult to obtain the effect of suppressing breakage and cracking. On the other hand, if the width exceeds 10 mm, the amount of useless transparent substrates increases, which is disadvantageous in terms of cost.

The antiglare layer can be formed by curing a coating solution printed by a gravure coating method. For the gravure coating printing, for example, a coating apparatus 30 as shown in FIG. 6 can be used. The coating apparatus 30 is configured such that a part of the outer peripheral surface of a gravure roll 32 having a rotating shaft extending in the horizontal direction is immersed in an antiglare agent A that is a slurry-like coating liquid stored in a storage tank 31. Yes. On the outer peripheral surface of the gravure roll 32, a concave portion having a certain depth extending in the circumferential direction except for both ends in the axial direction is provided over the entire circumference. The anti-glare agent A is filled in the concave portion by rotating it by a number. In addition, in order to ensure an exposed part in the both ends of the width direction of a transparent substrate as mentioned above, the width | variety of the axial direction of the gravure roll 32 of this recessed part is the elongate body printed using the said gravure roll 32. It is smaller than the width of the long resin film F ₀ of.

  On the outer peripheral surface of the gravure roll 32, the blade 33 is in contact with an angular position rotated about 90 ° out of the liquid surface of the antiglare agent A in the storage tank 31. The blade 33 is provided so that the cutting edge is parallel to the rotation center axis of the gravure roll 32 and extends linearly from end to end of the outer peripheral surface of the gravure roll 32. Since the outer peripheral surface of the roll 32 is recessed in a concave shape except for both ends, the cutting edge comes into contact only with both end portions of the outer peripheral surface. That is, the blade 33 removes the anti-glare agent A adhering to both ends of the outer peripheral surface of the gravure roll 32, and the surface of the anti-glare agent A filled in the concave portion has the same height as the both ends. Have a leveling role.

Further, a sub-roll 34 having a rotation center axis parallel to the rotation center axis of the gravure roll 32 is provided at a position in contact with the uppermost part of the outer peripheral surface of the gravure roll 32, and the coating is conveyed by roll-to-roll. The previous long resin film F ₀ is sandwiched between the sub roll 34 and the gravure roll 32. Thus, anti-glare agent A is filled in the concave portion after being leveled by the blade 33 is transferred to the surface of the long resin film F _0. In printing by this transfer, as described above, since the width of the long resin film F ₀ is wider than the width of the concave portion of the outer peripheral surface of the gravure roll 32 filled with the antiglare agent A, the long resin film F ₀ is formed. The anti-glare agent A is applied over the entire area excluding both ends in the width direction. A single strip-shaped antiglare layer extending in the longitudinal direction is formed on the entire surface of the long resin film F ₀ except for both ends in the width direction by curing the coating film by drying or the like as necessary. Can be formed.

  By the way, in the printing of the anti-glare agent by the wet process using the gravure roll as described above, in order to perform printing efficiently, it becomes a film formation target at the time of sputtering film formation in a subsequent roll-to-roll vacuum film forming apparatus. A wide resin film having a width in which two resin films are arranged in the width direction is first prepared, and this is printed on the entire surface, and then divided by a slit line extending in the longitudinal direction at the center in the width direction. It is common to take two items. Moreover, in order to print more efficiently, a wider resin film arranged in three or more rows in the width direction may be used.

  However, when printing is performed on a wide resin film in which two or more strips are arranged in the width direction using a gravure roll having concave portions on the outer peripheral surface except for both ends, for example, for two strips shown in FIG. In the case of the resin film 40, the entire surface excluding both end portions 40a in the width direction is covered with the antiglare layer 41. Therefore, when slitting with the slit line 42 indicated by the dotted line, each long resin film is one side in the width direction. The other end is not covered with the antiglare layer, but the other end is covered with the antiglare layer.

  Thus, for example, in the coating apparatus 30 in the case of performing two or three strips, a gravure is provided so that a plurality of concave portions extending in the circumferential direction are arranged adjacent to each other in the axial direction. It is preferable to use a roll. For example, FIG. 8 shows an example of a gravure roll 132 in which two concave portions 132a having a constant depth are provided over the entire circumference except for both end portions and the central portion in the axial direction on the outer peripheral surface. For example, after printing on a wide resin film for two strips using this gravure roll 132, a curing process such as drying is performed as necessary, and as shown in FIG. The anti-glare layer 46 can be formed except for both end portions 45a and the central portion 45b in the width direction. With respect to the double-stripping resin film 45 having the two anti-glare layers, both end portions in the width direction are slit by four slit lines 47 extending in the longitudinal direction at both end portions 45a and the central portion 45b. Two super birefringent films having an exposed portion can be obtained.

The coating of the antiglare agent is not limited to the case where the coating apparatus 30 shown in FIG. 6 is used, and a gravure coating type coating apparatus 35 provided with a film thickness adjusting rod 36 as shown in FIG. 10 may be used. . This coating apparatus 35 has a coating film formed by printing using a gravure roll 32 having one concave portion formed on the outer peripheral surface and a gravure roll 132 having a plurality of concave portions formed on the outer peripheral surface. to the coating film of the resin film F ₀ and it is capable of pressing the outer peripheral surface of the thickness adjusting rod 36 over the entire surface. Thereby, the film thickness of the coating film can be adjusted regardless of whether the coating film made of the anti-glare agent A is formed in a single line or a plurality of lines.

The outer peripheral surface of the thickness adjusting rod 36, the convex portions over the entire circumference at a position corresponding to the position where the coating film of the antiglare agent A by a gravure roll of the surface of the resin film F ₀ is formed form It is desirable that For example, in FIG. 11, two convex portions 36a extending over the entire circumference in the circumferential direction can be suitably used in the case of applying two coating films using the gravure roll 132 of FIG. A perspective view of the film thickness adjusting rod 36 is shown, and a convex portion 36a is formed in the film thickness adjusting rod 36 at an axial position where the concave portion 132 is formed in the gravure roll 132 described above. .

With this configuration, even when pressed a coating film made of antiglare agent A formed by printing with a gravure roll 132 by the film thickness adjusting rod 36, the coating film spreads excessively in the width direction of the resin film F ₀ Can be suppressed. As a result, exposed portions not covered with the antiglare layer can be secured at both ends in the width direction of the respective long resin films after being cut by the slit line 37 shown in FIG. 9 described above. Thus, by using the film thickness adjusting rod 36 having a convex portion on the outer peripheral surface, even when a resin film that does not substantially penetrate the coating liquid such as an antiglare agent is used, it is formed by printing with a gravure roll. Thus, it is possible to form an antiglare layer whose film thickness is adjusted while substantially maintaining the width of the coated film.

  The thus obtained transparent substrate such as a super-birefringent film coated with an antiglare layer composed of a cured layer excluding both ends in the width direction is then subjected to sputtering film formation treatment, wet plating treatment, and etching. The patterning process by is performed. As a result, a laminated structure in which the laminated film 102 patterned on both surfaces of the anti-glare-treated transparent substrate 101 as shown in FIG. 12 is provided.

  The laminated film 102 of this laminated structure includes a metal absorption layer 103 by a first layer sputtering method counted from the transparent substrate 101 side, a metal layer 104 by a second layer sputtering method and a wet plating method, and a third layer. The second metal absorption layer 105 formed by the sputtering method of the first layer, and the regular reflection R1 of the first metal absorption layer 103 on the back surface side through the transparent substrate 101 is reflected by the second metal absorption of the third layer on the front surface side. The specular reflection R2 of the layer 105 can be made substantially equal. Therefore, it becomes possible to make the reflection of the first metal absorption layer on the back surface side observed through the transparent substrate 101 inconspicuous.

  The laminated film on the long resin film covered with the above antiglare layer can be suitably formed with a roll-to-roll film forming apparatus 10 as shown in FIG. 13, for example. The film forming apparatus 10 shown in FIG. 13 is also called a sputtering web coater, and is coated with a curing agent along a roll-to-roll conveying path from the unwinding roll 12 to the take-up roll 24 through the can roll 16. A conveying means for conveying the long resin film F, a film forming means for continuously and efficiently forming a film on the surface when the long resin film F is wound around the outer peripheral surface of the can roll 16, and these means. It is mainly comprised from the vacuum chamber 11 to accommodate.

More specifically, the vacuum chamber 11 incorporates various devices (not shown) such as a dry pump, a turbo molecular pump, a cryocoil, and the like. After reducing the pressure to about ^-4 Pa, the pressure can be adjusted to about 0.1 to 10 Pa by introducing a sputtering gas. A known gas such as argon is used as the sputtering gas, and a gas such as oxygen is further added depending on the purpose. The shape and material of the vacuum chamber 11 are not particularly limited as long as they can withstand such a reduced pressure state, and various types can be used. A partition plate 11a is provided in the vacuum chamber 11 in order to isolate the space where the sputtering film formation is performed from the space where the transport roll group is provided.

  Among the roll-to-roll conveyance paths described above, the long resin film F on the upstream side of the free roll 13 and the can roll 16 that guide the long resin film F is provided on the conveyance path from the unwinding roll 12 to the can roll 16. The tension sensor roll 14 that measures the tension of the roller and the long speed resin film F guided to the outer peripheral surface of the can roll 16 are adjusted with respect to the peripheral speed of the can roll 16 so as to adhere to the outer peripheral surface. Rolls 15 are arranged in this order. Similarly to the above, the transport path from the can roll 16 to the take-up roll 24 is a motor driven post-feed roll 21 that adjusts the peripheral speed of the can roll 16 and the long resin film F downstream of the can roll 16. A tension sensor roll 22 for measuring the tension of the ink and a free roll 23 for guiding the long resin film F are arranged in this order.

  In the unwinding roll 12 and the winding roll 24, the tension balance of the long resin film F is maintained by torque control using a powder clutch or the like. The long resin film F unwound from the unwinding roll 12 by the rotation of the motor-driven can roll 16 and the motor-driven front feed roll 15 and the rear feed roll 21 that rotate in conjunction with the rotation of the motor-driven can roll 16 After being transported along a transport path defined by a group of rolls such as the roll 16, it is wound up by a winding roll 24.

  In the can roll 16, a coolant whose temperature is adjusted outside the vacuum chamber 11 circulates inside, and a process that applies a heat load from the surface is performed by the film forming means while being wound around the outer peripheral surface of the can roll 16. The long resin film F can be cooled from the back side. Four magnetron sputtering cathodes 17, 18, 19, and 20 are formed as film forming means along the conveyance path of the can roll 16 at a position facing the region around which the long resin film F is wound on the outer peripheral surface of the can roll 16. They are provided in this order. Each of the magnetron sputtering cathodes 17 to 20 is provided with a pair of gas discharge pipes 25a and 25b, 26a and 26b, 27a and 27b, and 28a and 28b that can discharge a reactive gas.

  Of these four magnetron sputtering cathodes 17-20, for example, a target for forming a metal absorption layer is provided on the target of the first two cathodes 17-18, and a target for forming a metal layer is provided on the target of the remaining two cathodes 19-20. By providing, a metal absorption layer and a metal layer made of a metal oxide can be continuously formed on one surface of the long resin film F. In addition, since nodule (growth of foreign matter) may occur on a target when a metal absorption layer or a metal layer is formed by sputtering using a plate-like target, no nodule is generated and the use efficiency of the target Also, a high cylindrical rotary target may be used.

  Similarly, when the metal absorption layer and the metal layer are continuously formed on the other surface of the long resin film F, the roll of the long resin film F formed on the one surface is a take-up roll. The film may be formed in the same manner as described above except that it is detached from 24 and attached to the unwinding roll 12, and the unwinding roll 12 is rotated in the direction of the white arrow shown in FIG. Thereby, the laminated body substrate of the laminated structure with few dispersion | variation in quality which can be used suitably for the base material of electrode substrate films, such as for touch panels, can be produced.

  In general, when a metal oxide target is used as a target for forming a metal absorption layer, the film forming speed is slow and not suitable for mass production. Therefore, a Ni-based metal target (metal material) capable of high-speed film formation is used. A reactive film-forming method such as reactive sputtering introduced while controlling a reactive gas containing oxygen is performed. In addition, since the metal absorption layer becomes transparent when the oxidation of the metal oxide constituting the metal absorption layer formed by the reactive film formation method proceeds excessively, the oxidation level is suppressed to such a level that it becomes a blackened film visually. Is desirable. When the metal absorption layer is formed by the reactive film formation method, each metal element forms a non-stoichiometric compound with oxygen atoms, and the non-stoichiometric oxide is visually black.

  As a method of controlling the reactive gas, (1) a method of releasing a reactive gas at a constant flow rate, (2) a method of releasing a reactive gas so as to keep the pressure in the vacuum chamber constant, ( 3) Method of releasing reactive gas so that the impedance of the sputtering cathode is constant (impedance control), and (4) Method of releasing reactive gas so that the plasma intensity of sputtering is constant (plasma emission control). The following four methods are known. In addition to the sputtering method using the magnetron sputtering cathodes 17 to 20 as shown in FIG. 13, the reactive film formation method includes dry plating methods such as ion beam sputtering, vacuum deposition, ion plating, and CVD.

  With the film forming apparatus 10 described above, for example, a laminated film composed of the metal absorption layer 51 and the metal layer 52 can be formed on both surfaces of the transparent substrate 50 subjected to the antiglare treatment as shown in FIG. The metal absorption layer 51 is preferably composed of a non-stoichiometric metal oxide layer, which is composed of Cu, Ni, or Ni with Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Cu, And a metal material made of a Ni-based alloy to which one or more elements selected from the group consisting of Zn are added, can be formed by a reactive film formation method in a reactive gas atmosphere containing oxygen. In the case of a Ni-based alloy, a Ni—Cu alloy is preferable.

  On the other hand, the metal layer 52 can be formed in a general inert gas atmosphere, and the constituent material thereof is not particularly limited as long as it is a metal having a low electric resistance value. , Al, V, W, Ta, Si, Cr, Ag-based Cu alloy with one or more elements added, or Ag alone, or Ag with Ti, Al, V, W, Ta, Si, Cr And Ag-based alloys to which one or more elements selected from Cu are added. Among these, Cu alone is desirable from the viewpoint of circuit pattern workability and resistance.

  The film thickness of the metal absorption layer 51 is preferably about 15 to 30 nm. The film thickness of the metal absorption layer 51 affects the electrical characteristics and is not determined only by optical requirements. However, it is preferable to set the film thickness to a level at which transmitted light cannot be measured. On the other hand, the film thickness of the metal layer 52 is preferably 50 to 5000 nm, and more preferably 3 μm (3000 nm) or less from the viewpoint of workability for patterning so as to form a predetermined wiring pattern. In order to increase the thickness of the metal layer 52, the metal layer 52 may be further formed on the metal layer 52 formed by the dry plating method using a wet plating method such as an electroplating method. That is, as shown in FIG. 15, after the metal absorption layer 51 and the metal layer 52 are formed on both surfaces of the antiglare-treated transparent substrate 50 by a dry plating method, the metal layer 53 is formed on the metal layer 52 by a wet plating method. May be formed. The metal layer 53 formed by this dry plating method preferably has a film thickness of 15 μm or less.

  A second metal absorption layer may be further formed on the metal layer 53. That is, as shown in FIG. 16, after the metal absorption layer 51 having a film thickness of, for example, 15 to 30 nm and the metal layer 52 having a film thickness of, for example, 50 to 1000 nm are formed on both surfaces of the transparent substrate 50 subjected to the antiglare treatment by a dry plating method. Alternatively, the metal layer 53 may be formed by a wet plating method, and the second metal absorption layer 54 having a film thickness of, for example, 15 to 30 nm may be formed on the metal layer 53 by a dry plating method. This second metal absorption layer is selected from Cu simple substance, Ni simple substance, or Ni, Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, Cu, Zn similarly to the metal absorption layer 51. It is obtained by forming a film by a reactive film formation method in a reactive gas atmosphere containing oxygen using a metal material made of a Ni-based alloy to which elements of more than one species are added.

  By forming a metal absorption layer on both sides of the metal layer thickened by the dry plating method and the wet plating method in this way, when the electrode substrate film produced using this laminate substrate is incorporated into the touch panel, it is made of metal. The circuit pattern having a mesh structure composed of the laminated thin wires can be made difficult to see by reflection. Even when an electrode substrate film is produced using a laminate substrate obtained by forming a metal absorption layer and a metal layer only on one side of a transparent substrate made of a long resin film, it is difficult to see a circuit pattern from the transparent substrate. can do. The optical constant (refractive index, extinction coefficient) at each wavelength of the metal absorption layer is greatly influenced by the degree of reaction, that is, the degree of oxidation, and is not determined only by a metal material made of a Ni-based alloy. In the case of a Ni—Cu alloy, depending on the mixing ratio of Ni and Cu, a metal absorption layer that is visually recognized as a black film even if a method that does not use a reactive film formation method (that is, a film formation method that does not use a reactive gas). May be deposited.

  An electrode substrate film can be obtained by patterning the laminated film of the laminate film produced above to form a metal laminated thin wire having a line width of, for example, 20 μm or less. For example, an electrode substrate film as shown in FIG. 17 can be obtained by patterning the laminated film of the laminate film shown in FIG. 16 by etching or the like. The electrode substrate film shown in FIG. 17 has a circuit pattern having a mesh structure made of, for example, metal multi-layer thin wires having a line width of 20 μm or less provided on both surfaces of the anti-glare-treated transparent substrate 50. The thin line is composed of a first metal absorption layer 51a, a second metal layer 52a, 53a, and a third metal absorption layer 54a as counted from the transparent substrate 50 side.

  Thus, it can use for a touch panel by making the electrode (wiring) pattern of an electrode substrate film into stripe form or a grid | lattice form, and the metal lamination | stacking thin wire in this case is maintaining the laminated structure of the said laminated body film. Therefore, even under high-luminance illumination, circuit patterns such as electrodes provided on the transparent substrate are extremely difficult to visually recognize. That is, when reactive sputtering film formation is performed in a reactive gas atmosphere obtained by adding oxygen to argon, a black film is obtained as a metal absorption layer, so that it becomes possible to suppress the reflectance of light when irradiated, Therefore, a circuit pattern such as an electrode obtained by etching the metal absorption layer is hardly visible under high-intensity illumination. Furthermore, as described above, since the anti-glare layer having a haze value of 10% or less is preferably provided on the transparent substrate made of a resin film, the visibility of the flat display panel is adversely affected when the image of the flat display panel is observed through the electrode substrate film. It becomes difficult to exert.

  A known subtractive method can be used as a method for forming the electrode substrate film by patterning the laminate substrate. In the subtractive method, a photoresist film is formed on the laminate film surface of the laminate substrate, and exposure and development processes are performed so that the photoresist film remains at a position where an electrode pattern is to be formed, and the laminate film exposed from the photoresist film. In this method, the portion is removed by chemical etching to form an electrode pattern. As an etching solution for the above chemical etching, an aqueous solution of ferric chloride or an aqueous solution of cupric chloride can be used.

  As mentioned above, although the specific example of the printing method to the elongate body of this invention was demonstrated taking the case of producing a laminated body film as an example, the use of a laminated body film is limited to the electrode substrate film for touch panels. It can also be used for flexible wiring boards and the like. When used for a flexible wiring board, each of both surfaces of the laminate film has a laminated structure of at least two layers. For example, the first layer is Ni, Ti, Al, V, W, Ta, Si, Cr, Ag. , Mo, Cu, and Zn. It is preferable that the second alloy layer is a Ni-based alloy layer to which one or more elements selected from the group consisting of Zn, and a second layer is composed of a metal layer made of a copper layer.

  Furthermore, the printing method of the long body of the present invention is not limited to the printing method for providing an antiglare layer on a resin film such as a super birefringent film, and the long body to be printed is an electric substrate film. In addition to the transparent resin film used in the laminate film for use, when transparency is not required, a colored film such as a polyimide film can be used. Further, the present invention can also be applied to a metal strip or the like. For example, it can be applied to a case where a slurry of a complex oxide powder is printed on a surface of a long copper foil or the like.

  As a long resin film for two strips, a Toyobo-made super birefringent film (model number: Cosmo Shine SRF film) with a thickness of 50 μm, a width of 1200 mm, and a length of 1200 m is prepared. The antiglare layer was coated except for the central part. A gravure coating type coating apparatus 30 as shown in FIG. 6 was used for coating. The gravure roll has a depth of 3 mm and a width of 580 mm, and is recessed in a concave shape over the entire circumference, except for the position of the central portion 20 mm in the axial direction and both ends as shown in FIG. A gravure roll 132 having two concave portions 132a was used. The anti-glare treatment agent A in which a silica filler having a diameter of 1 μm was dispersed in a UV curable acrylic resin was stored in the storage tank 31 so that the gravure roll 132 was partially immersed.

Next, sandwiched between the auxiliary roll 34 of the reverse rotation to the gravure roll 132 to as long resin film F ₀ to rotate the gravure roll 132 while adjusting the rotational speed are transported by a roll-to-roll. Thus it was printed by directly transferring the two concave portions 132a antiglare coating agent A filled in the outer peripheral surface of the gravure roll 132 to the long resin film surface of the F _0. As a result, a coating film made of the antiglare coating agent A is formed on the long resin film F ₀ in a region excluding the 20 mm width portion at the center in the width direction and the 10 mm portions from the respective edges at both ends in the width direction. did. The film thickness of the coating film was adjusted to about 1 μm by adjusting the rotation speed of the gravure roll 132.

  After the coating film made of the antiglare coating agent A was cured by drying to form an antiglare layer, an antiglare layer was also formed on the other surface in the same manner. When the pencil hardness of the obtained antiglare layer was evaluated based on JIS K5600-5-4 1999, it was intermediate between HB and H. The obtained super birefringent film coated with the antiglare layer was divided into two with a slit in the center in the width direction, and a film forming apparatus (sputtering web coater) as shown in FIG. 13 for one of them. 10 was used to form a laminated film on both sides.

  A stainless steel cylindrical member having an outer diameter of 600 mm and a width of 750 mm was used for the can roll 16 of the film forming apparatus 10, and the outer peripheral surface thereof was subjected to hard chrome plating. The front feed roll 15 and the rear feed roll 21 were each made of a stainless steel cylindrical member having an outer diameter of 150 mm and a width of 750 mm, and the surfaces thereof were also plated with hard chrome. The magnetron sputtering cathodes 17 and 18 were attached with a Ni—Cu target for the metal absorption layer, and the magnetron sputtering cathodes 19 and 20 were attached with a Cu target for the metal layer.

The super birefringent film covered with the antiglare layer made of the above hardened layer was set on the unwinding roll 12, and the tip was wound around the winding roll 24 through various roll groups. The temperature of the refrigerant circulating in the can roll 16 was controlled at 0 ° C. In this state, the inside of the vacuum chamber 11 was evacuated to 5 Pa by a plurality of dry pumps, and then evacuated to 3 × 10 ⁻³ Pa using a plurality of turbo molecular pumps and a cryocoil. Then, the super birefringent film coated with the antiglare layer was transported at 2 m / min to perform sputtering film formation.

  At the time of sputtering film formation, the magnetron sputtering cathodes 17 and 18 for forming the metal absorption layer form argon gas of 500 sccm and oxygen gas from the gas discharge pipes 25 a and b and 26 a and b respectively arranged in the vicinity thereof. Introduced at a flow rate of 50 sccm, power control was performed so as to obtain a 30 nm thick Ni—Cu oxide layer. On the other hand, in the magnetron sputtering cathodes 19 and 20 for forming a metal layer (copper layer), argon gas is introduced at a flow rate of 500 sccm from the gas discharge pipes 27 a and b and 28 a and b arranged in the vicinity thereof. The power was controlled so that a Cu layer with a thickness of 80 nm was obtained on the Ni—Cu oxide layer.

  After the sputtering film formation on one side of the super birefringent film was completed, the atmosphere was introduced into the vacuum chamber 11, and the super birefringent film wound around the take-up roll 24 was removed and set on the unwind roll 12. A sputtering film was also formed on the other surface in the same manner. After the sputtering film formation on both sides is completed, a film is formed on both surfaces by electroplating so that the copper thickness becomes 1 μm, and the film thickness of 30 nm is formed on both surfaces by the same method as described above using the film formation apparatus 10 again. Two metal absorption layers were formed by sputtering. In this way, a laminated film composed of the first Ni-Cu oxide film, the second Cu film, and the third Ni-Cu oxide film is laminated on both surfaces of the super birefringent film. A laminate film of Sample 1 was prepared.

Further, in place of the gravure roll 132 shown in FIG. 8, one concave portion having a width narrower than the width of the super-birefringent film F ₀ is formed over the entire circumference in a region excluding both ends of the outer peripheral surface. except that by using a gravure roll region excluding the both widthwise end portions of the ultra-birefringent film F ₀ were coated with anti-glare layer was in the same manner as the sample 1 of the above prepared laminated film of sample 2. Then, the laminated films of Samples 1 and 2 were subjected to patterning using an aqueous ferric chloride solution as an etching solution to produce the electrode substrate films of Samples 1 and 2, respectively.

  When both electrode substrate films after patterning were confirmed visually, the electrode substrate film of Sample 2 was not cracked because an antiglare layer was not formed at one end in the width direction. Since an anti-glare layer was formed on one end, a crack that was thought to have been caused by an impact such as a change in tension occurred. On the other hand, since the electrode substrate film of Sample 1 did not form antiglare layers at both ends of the super birefringent film, no cracks were found. Thus, instead of covering the antiglare layer from end to end in the width direction, the surface hardness decreased slightly by covering the antiglare layer except for both ends, so it is estimated that cracking was suppressed. The In addition, the electrode substrate films of Samples 1 and 2 could hardly visually recognize the electrode on the back side through the transparent substrate under high luminance illumination. Therefore, it turned out that the electrode substrate film of the sample 1 is more suitable as a “touch panel” installed on the surface of an FPD (flat panel display).

A Anti-glare agent C Crack F ₀ Long resin film before coating with ₀ hardened layer F Long resin film with hardened layer covered s Test piece h Integrating sphere i Diffuser plate j Light k Receiver T ₀ Total light transmittance T ₁ Scattered light transmittance R ₁ Specular reflection of metal absorption layer through transparent substrate R ₂ Specular reflection of second metal absorption layer 1, 101 Transparent substrate 2, 102 Laminated film 3, 103 Metal absorption layer 4, 104 Metal layer 5, 105 Second metal absorption Layer 6 Super birefringent film 7 Transparent substrate 8 Anti-glare layer 9, 9A Fine particles 10 Film forming device 11 Vacuum chamber 12 Unwinding roll 13, 23 Free roll 14, 22 Tension sensor roll 15 Front feed roll 16 Can roll 17, 18, 19 , 20 Magnetron sputtering cathode 21 Rear feed roll 24 Winding roll 25a · b, 26a · b, 27a · b, 28 a, b Gas discharge pipe 30, 35 Coating device 31 Storage tank 32, 132 Gravure roll 132a Concave part 33 Blade 34 Sub roll 36 Film thickness adjusting rod 36a Convex part 40, 45 Double-stripping resin film 40a, 45a Both end part 45b Central portion 41, 46 Anti-glare layer 42, 47 Slit line 51 Metal absorption layer 52 Metal layer (copper layer) formed by dry film formation method
53 Metal layer (copper layer) formed by wet film formation method
54 Second metal absorption layer 51a Patterned metal absorption layer 52a Patterned metal layer (copper layer) formed by dry deposition method
53a Metal layer (copper layer) formed by wet film-forming method patterned
54a Patterned second metal absorption layer

Claims (7)

It is a printing method on a long body that forms at least one strip-shaped coating film extending in the longitudinal direction excluding both ends in the width direction on at least one surface of the long body,
Using a gravure roll provided with a concave portion provided on the outer peripheral surface over the entire circumference, corresponding to the position where the pre-coating film is formed from end to end in the width direction of the elongated body A printing method for a long body, wherein a coating liquid for forming a coating film is printed on the long belt.   The one or more strips are a plurality of strips, and the long body is cut in the longitudinal direction in an uncoated region existing between adjacent coating films in the width direction of the long body. The printing method to the elongate body of Claim 1.   The method for printing on a long body according to claim 1 or 2, wherein the coating film is cured after the printing to form a cured layer.   A convex portion provided corresponding to a position where the coating film is formed from end to end in the width direction of the elongated body before the coating film formed by the printing is cured is an outer peripheral surface. The film thickness of the peritoneum is adjusted by bringing the convex portion of the film thickness adjusting rod provided over the entire circumference into contact with the coating film. The printing method to the elongate body of Claim 1.   5. The printing method for a long body according to claim 1, wherein the peritoneum is not formed in a range of 1 mm to 10 mm from both ends in the width direction of the long body.   The method for printing a long body according to any one of claims 1 to 5, wherein the hardened layer is harder than the resin film and softer than a pencil hardness H.   The method for printing a long body according to any one of claims 1 to 6, wherein the long body is a super-birefringent resin film having a tensile strength in a longitudinal direction of 100 MPa or less.

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